Method for producing piezoelectric ceramics

ABSTRACT

A method for producing piezoelectric ceramics of a Pb(Sn.sub.α Sb 1- α)O 3  -PbTiO 3  system is disclosed which comprises providing a piezoelectric ceramic composition expressed by the general formula: 
     
         xPb(Sn.sub.α Sb.sub.1-α)O.sub.3 -PbTiO.sub.3 
    
     wherein subscripts α, x and y are mole fractions of the respective components and have the following values, x+y=1.00, 1/4≦α≦3/4, 0.01≦x≦0.40, and 0.60≦y≦0.99, forming powder of the composition into forming bodies, and firing the forming bodies in an oxygen atmosphere containing not less than 80 vol % of oxygen. The firing in the oxygen atmosphere is effected at a temperature not less than 1000° C. A part of lead in the composition may be replaced with not more than 20 atomic percent of at least one metal selected from the group consisting of Ba, Ca, Sr and Cd. The composition may contain a small amount of Mn, Mg and/or Cr. Fine dense ceramics with low porosity, small average size and fine grain size are produced which can be applied to various electronic parts.

BACKGROUND OF THE INVENTION

The present invention relates to a method for producing piezoelectric ceramics and, more particularly, to a method for producing piezoelectric ceramics of a system Pb(Sn.sub.α Sb₁₋α)O₃ -PbTiO₃ with α ranging from 1/4 to 3/4.

Piezoelectric ceramics such as barium titanate (BaTiO₃), lead zirconate titanate (Pb(Zr, Ti)O₃), lead titanate (PbTiO₃) and their modifications are now being manufactured and used in the electronic fields as electronic parts such as acoustic surface wave elements including acoustic surface wave filters, acoustic surface wave delay lines and acoustic surface wave discriminators; ceramic filters; ceramic resonators; ceramic vibrators; piezoelectric ignition elements; or piezoelectric ceramic transformers.

Such piezoelectric ceramics have generally been manufactured in the following processes; Weighing-Wet-Mixing-Drying-Calcination-Wet-Crushing (with binder)-Drying-Granulation-Forming-Firing. The most important process affecting the quality of the final products is firing which is effected in an air. In order to prevent the evaporation of lead oxide from the composition during firing, it is the usual practice to fire forming bodies in a closed saggar made of a material which is unreactive to PbO and has no permeability of PbO, such as alumina or magnesia. In addition, PbO powder or mixed powder of PbO and ZrO₂ is put in the sagger to form a lead oxide atmosphere surrounding the forming bodies.

However, the piezoelectric ceramic produced by the above normal air sintering method have relatively high porosity, and large average pore size ranging from 5 to 15 microns. Because of their relatively high porosity and large average pore size, their regular use is impossible for some specific applications. For example, when a ceramic material is applied to acoustic surface wave filters having a general construction of FIG. 1 and comprising a piezoelectric ceramic substrate 1 and interdigital electrodes 2 and 3 formed thereon, the porosity and pore size must be small as much as possible since the width a of the electrodes decreases with the increase of operating frequencies of the filters. Assuming that the acoustic surface wave velocity is 2400 m/sec, a filter designed to be operated at a frequency of 58 MHz is required to have the interdigital electrodes with a width a of about 10 microns since the wave length is about 41 microns. When split electrodes 4 shown in FIG. 1 are used to restrain the Triple transit Echo (Ref: PROPERTIES OF SPLIT-CONNECTED AND SPLIT-ISOLATED MULTISTRIP COUPLER, A. J. Devris et al. "1975 Ultrasonics Symposium Proceedings" IEEE cat. #75 CHO 994-4SU), they are required to have a width 4a of about 5 microns. Accordingly, if the piezo-electric ceramics used have high porosity, or if the pores connected to the surface of the ceramics are larger than 2 microns, the pores would cause the disconnection of the electrodes, in particular the split electrodes 4, thus making it difficult to produce acoustic surface wave filters for very high frequency applications.

When the piezoelectric ceramics with high porosity are applied to ceramic vibrators, ceramic filters, and the like, it is impossible to obtain the products with high quality because of the low strength of the ceramics. In the vibrators, it is the usual practice to apply a high voltage to obtain large amplitudes of the vibration. In this case, if the ceramics have a strain strength lower than the strain stress which occurs due to the vibration of the ceramics, it results in the breakdown of the ceramics.

In addition, in preparing miniaturized, ladder type filters which comprises a pair of resonators (a) and (b) as shown in FIG. 2 it is the usual practice to reduce the thickness of ceramic bodies for the 1st or 2nd resonator (a) or (b) to make the capacitance ratio between them large. Since there is a regular relation between the thickness and the mechanical strength of the ceramics, the ceramics with low strength make it difficult to keep the highest quality level of the product. In the resonators for high temperature applications, designed to be operated at temperatures ranging from 100 to 200° C., it is necessary to use ceramics with high thermal shock resistance in addition to the high strength. If the ceramics have high porosity, it leads to serious problems described later. In the thickness expansion mode filters, its center frequency is inverse to the thickness of the ceramics, so that the strength of ceramics has great influence on the quality of the product used in high frequencies. The most critical factors affecting on the strain strength and thermal shock resistance are the grain size and porosity, so that it is necessary to use ceramic materials with fine grain size and low porosity.

As a method for the fabrication of piezoelectric ceramics with low porosity, there have been proposed a hot-pressing method and a hot-isostatic pressing method. However, both the methods have not been developed for mass-production, resulting in the considerable rise of manufacturing cost.

In addition to the above processes, there is a few specific processes using oxygen atmosphere sintering technique. For example, Gray S. Snow reported high-lead-oxide atmosphere sintering technique for producing transparent electrooptic lanthanum modified lead zirconate titanate ceramics, which is disclosed in "Fabrication of Transparent Electrooptic PLZT Ceramics by Atmosphere Sintering" (Journal of The American Ceramic Society, 56 (2) 91-96 (1973)). In this process, green forming bodies of chemically prepared PLZT powder with excess PbO are sintered in an atmosphere containing oxygen and a very high partial pressure of lead oxide. The excess PbO is present as a liquid phase at the grain boundaries of the bodies at the sintering temperature, and this liquid phase enhances densification and pore removal by promoting mass transport through a liquid phase of lead oxide along the grain boundaries to the pores. Although this process makes it possible to produce PLZT ceramics with low porosity, it has a serious disadvantage such that very large pores remain in the sintered ceramics because of the coalescence of small pores into large ones.

As described above, various attempts have been made to produce lead-containing piezoelectric ceramics with low porosity together with small grain size, but much satisfactory results are not yet obtained.

SUMMARY OF THE INVENTION

It is therefore an object of the present invention to provide a method for producing piezoelectric ceramics which fully satisfy the aforesaid requirements.

Another object of the present invention is to provide a method for producing piezoelectric ceramics of a Pb(Sn.sub.α Sb₁₋α)O₃ -PbTiO₃ system with very low porosity, small average pore size and fine grain size.

Still another object of the present invention is to provide piezoelectric ceramics of a Pb(Sn.sub.α Sb₁₋α)O₃ -PbTiO₃ system which make it possible to produce various electronic parts with high quality.

According to the present invention, there is provided a method for producing piezoelectric ceramics of a system Pb(Sn.sub.α Sb₁₋α)O₃ -PbTiO₃, which comprises providing a piezoelectric ceramic composition expressed by the general formula:

    xPb(Sn.sub.α Sb.sub.1-α)O.sub.3 -yPbTiO.sub.3

wherein subscripts α, x and y are mole fractions of the respective components and have the following values, x+y=1.00, 1/4≦α≦3/4, 0.01≦x≦0.40, and 0.60≦y≦0.99, forming powder of said composition into forming bodies, and firing said bodies in an oxygen atmosphere containing not less than 80 vol% oxygen.

Preferably, the oxygen atmosphere is kept at a temperature not less than 1000° C., and the highest temperature at the final stage of the firing ranges from 1100° to 1350° C.

In order to obtain fewer pores and higher strength, it is preferred to use a oxygen atmosphere containing not less than 95 vol% of oxygen.

The above composition may further contain not more than 5 wt% of manganese oxide, not more than 5 wt% of magnesium oxide and/or not more than 5 wt% of chromium oxide as one or more assistant components. Further, a part of lead in the composition may be replaced with not more than 20 atomic % of at least one element selected from the group consisting of Ba, Ca, Sr and Cd.

DETAILED DESCRIPTION OF THE INVENTION:

According to the invention, piezoelectric ceramics of a system Pb(Sn.sub.α Sb₁₋α)O₃ -PbTiO₃ with α ranging from 1/4 to 3/4 are produced in the following manner.

Raw materials are weighed according to the formula xPb(Sn.sub.α Sb₁₋α)O₃ -yPbTiO₃ with α ranging from 1/4 to 3/4, x ranging from 0.01 to 0.40, and y ranging from 0.60 to 0.99. If necessary, one or more assistant constituents (i.e., Mn, Mg, Cr) may be incorporated into the resulting mixture. These raw materials may be oxides, carbonates, hydroxides, oxalates and so on and so forth. The raw material mixture is wet-mixed in a ball mill for at least 10 hours. After drying, the resulting mixture is calcined at a temperature of 600° to 900° C. for a few hours. The resultant calcined body is wet-ground together with a suitable organic binder. The resulting slurry is dried, granulated, and then formed into green ceramic ware or forming bodies such as discs, plates and the like at a pressure of 700 to 1000 kg/cm². The forming bodies are fired in an oxygen atmosphere containing not less than 80 vol% oxygen, while keeping a low partial pressure of lead in the atmosphere constant. The highest temperature of this high oxygen concentration firing ranges from 1100° to 1350° C.

In the composition of the system Pb(Sn.sub.α Sb₁₋α)O₃ -pbTiO₃ with α ranging from 1/4 to 3/4, there is formation of an intermediate phase which has a pyrochlore crystal structure with oxygen defect, expressed by the formula Pb₂ Sn₂α Sb₂₋₂α O₇₋α, at the grain boundaries of the forming body in the early stages of firing, in addition to the formation of a perovskite phase of PbTiO₃. This pyrochlore phase is present up to an elevated temperature of about 1200° C. at which the formation of the final product occurs, and affects the microstructure of ceramic and the properties thereof. As will be understood from the descriptions with reference to FIGS. 3 to 8, the progress of sintering is assured by the diffusion of oxygen in the closed pores through the oxygen defect in the Pb₂ Sn₂α Sb₂₋₂α O₇₋α° phase. The oxygen defect of the pyrochlore phase promotes the transfer of oxygen ions at grain boundaries, thus making it possible to producing fine, dense ceramics. At the final stage of the firing, the pyrochlore phase (Pb₂ Sn₂α Sb₂₋₂α O₇₋α) transformes into a perovskite phase, Pb(Sn.sub.α Sb₁₋α)0₃.

In order to obtain ceramics with very low porosity and fine grain size not more than 10 microns, the firing body are preferably made using fine-grained materials with average grain size of not more than 4 microns, and fired at temperatures of 1000° to 1200° C.

In the sintering atmosphere with high oxygen concentration more than 80 vol% which is not less than 4 times that in air, the mobility of oxygen ions through the oxygen defect of the pyrochlore phase increases abruptly, resulting in the formation of a dense ceramic with the considerably decreased number of small pores.

If an oxygen atmosphere containing not less than 95 vol% of oxygen is used, it enables to obtain fewer pores and higher mechanical strength. The firing may be scheduled in two ways, one of which is that the high oxygen concentration atmosphere firing is initiated just before the occurrence of colosed pores, in other words, at about 1000° C. The other is that the high oxygen concentration atmoshpere firing is effected through the firing process. In both cases, the transfer of oxygen in the closed pore is sufficiently achieved through the oxygen defect in the pyrochlore phase which present at the grain coundaries, thus making it possible to produce fine, dense ceramics. In brief, in order to obtain fine, dense ceramics, it is sufficient initiated at a temperature just before the occurrence of closed pores. Accordingly, in the former schedule, the forming bodies may be fired in air before the occurrence of closed pore, or after the end of the sintering.

The piezoelectric ceramics to be produced by the method of the present invention have been limited to those having the aforesaid composition with or without a certain amount of one or more assistant components, for the following reasons.

If the content of the component Pb(Sn.sub.α Sb₁₋α)O₃ is less than 0.01 mole, no pyrochlore crystal phase with oxygen defect which contributes to promotion of sintering is formed during the firing even in the high oxygen concentration atmosphere. If the content of Pb(Sn.sub.α Sb₁₋α)O₃ exceeds 0.40 mole, it is difficult to obtain high electromechanical coupling coefficient

The reason why α is limited within the range of 1/4 to 3/4 is that α outside of this range results in the difficulty is sintering because of the formation of other new pyrochlore phase (Pb₂ Sb₂ O₇, β<1/4) or that of PbSnO₃ with no oxygen defect, and makes it impossible to obtain sufficiently porefree ceramics even when the composition is fired in the high oxygen concentration atmosphere.

The addition of Mn contributes to improvement in the electromechanical coupling coefficient, but the addition more than 5.0 wt% when converted into MnO₂ causes the difficulty in sintering and polarization. The addition of Mg restrains the grain growth and contributes to improvement in the temperature characteristics of center or resonant frequency of filters or resonators, but the addition more than 5.0 wt% when converted into MgO causes the difficulty in sintering and polarization. The addition of Cr contributes to improvement in the heat aging characteristics, i.e., resistance to heat aging, but addition more than 5.0 wt% when converted into Cr₂ O₃ causes the difficulty in sintering and polarization. Although these assistant components exert their respective effects by incorporating them into the composition in an amount more than 0.5 wt% in terms of their respective oxide forms, the compositions containing less than 0.5 wt% are also included in the scope of the present invention.

BRIEF DESCRIPTION OF THE DRAWINGS

The invention will be further apparent from the following description with reference to examples and accompanying drawings, in which:

FIG. 1 is a schematic perspective view of an acoustic surface wave filter;

FIG. 2 is a circuit diagram of a ladder type ceramic filter;

FIG. 3 is a schematic section view of an alumina tube furnace used for embodying the present invention;

FIGS. 4 and 5 are X-ray diffraction patterns of reaction products obtained from the Pb(Sn.sub.α Sb₁₋α)O₃ -PbTiO₃ system;

FIG. 6 is a graph showing relative X-ray intensity of the reaction products for Pb(Sn.sub.α Sb₁₋α)O₃ -PbTiO₃ system as a function of temperature;

FIG. 7 is an X-ray diffraction pattern of a pyrochlore crystal phase resulting from the system Pb(Sn.sub.α Sb₁₋α)O₃ with α=1/2;

FIGS. 8 and 9 are scanning electron micrographs showing microstructures of Pb(Sn.sub.α Sb₁₋α)O₃ PbTlO₃ ceramics produced by the method of the present inventions;

FIG. 10 is a scanning electron micrograph showing a microstructure of a ceramic of the system PbTiO₃ --0.5 wt% Al₂ O₃ --0.5 wt% SiO₂ ;

FIGS. 11 to 14 are reflecting micrographs showing microstructures of various ceramics with polished surfaces; and

FIGS. 15 and 16 are scanning electron micrographs showing microstructures of piezoelectric ceramics produced according to the present invention and the prior art.

Before describing the practical examples of the present invention, physical arrangement and use of an alumina tube furnace used for embodying the present invention are briefly described below for making it easy to understand the invention.

Referring to FIG. 3, an alumina tube furnace for embodying the present invention comprises an alumina tube 11 adapted to be closed by plugs 14 and 15 at its both ends and heated by a heater 13 surrounding the alumina tube 11. In the alumina tube 11, there is an alumina sagger 12 in which PbO and ZrO₂ powder is placed to form a lead oxide atmosphere which prevent the evaporation of PbO from the composition during firing. Numeral 16 is an inlet for feeding oxygen gas or a mixture of oxygen and air into the alumina tube 11, and numeral 17 is an outlet for exhausting atmosphere gas in the alumina tube 11. The temperature in the furnace is taken by a thermocouple 18.

Using the above furnace, the firing is conducted in the following manner: The forming bodies are placed in the alumina sagger 12 containing a suitable amount of PbO and ZrO₂ powder which prevent the evaporation of PbO from the forming bodies. After making the alumina tube 11 shut tight, the alumina tube 11 is heated by the heater to an elevated temperature ranging from 1000° to 1350° C., while introducing oxygen atmosphere gas containing not less than 80 vol% oxygen. The atmosphere-gas flow rate is selected within the range of 1 to 100l/hr so that the lead oxide atmosphere in the alumina saggar is kept constant and, that the vapor pressure of PbO in the sagger is kept at a value sufficient to prevent the evaporation of PbO from the composition but insufficient to cause the diffusion of PbO into the composition during firing.

EXAMPLE 1

Fine powder of PbO, TiO₂, SnO₂, Sb₂ O₃, MnO₂, Mg(OH)₂, Cr₂ O₃, BaCO₃, CaCO₃, SrCO₃ and CdCO₃ were used as raw materials. These materials were weighed according to the above general formula to provide piezoelectric ceramic compositions having compositional proportions shown in Table 1, and then wet-milled in a ball mill for 20 hours. The resultant slurry was dried, and calcined for 2 hours at 700 to 900° C. The calcined body was wet-ground, together with a suitable organic binder, dried and then granulated to provide fine-grained powder. The resultant powder was formed into plates of 50 mm square and 1.2 mm thick, or disks of 22 mm diameter and 1.2 mm thick at a pressure of 1000 kg/cm². Using the alumina tube furnace shown in FIG. 3, the green wafers and disks were fired at about about 1200° C. for 2 hours in an oxygen atmosphere. The concentration of oxygen in the atmosphere is shown in Table 1 .

                  TABLE 1                                                          ______________________________________                                                      Basic                                                                          Component                                                                      (mol      Repl.              O.sub.2                              Sample        fraction)                                                                               Element Ass. Component                                                                            conc.                                No.   α                                                                               x      y    (atomic %)                                                                             Mn   Mg   Cr   (%)                            ______________________________________                                         1*    --     0.00   1.00     --    --   --   --   100                          2     1/2    0.01   0.99     --    --   --   --   100                          3     1/4    0.01   0.99     Ba:5.0                                                                               --   --   --    90                          4     1/4    0.01   0.99     Sr:5.0                                                                               0.05 --   --    90                          5     3/4    0.01   0.99     Ca:5.0                                                                               --   --   --   100                          6     3/4    0.01   0.99     Cd:5.0                                                                               --   0.05 --   95                                                        Ba:6.0                                            7     9/20   0.05   0.95           --   --   --   100                                                       Sr:6.0                                            8     1/2    0.05   0.95     --    1.0  1.0  1.0  100                                                       Ba:6.0                                            9     1/4    0.15   0.85     Ca:6.0                                                                               --   --   --   100                                                       Sr:6.0                                                                         Ba:6.0                                            10    1/4    0.15   0.85     Sr:6.0                                                                               --   --   0.05  80                                                       Cd:6.0                                                                         Ba:6.0                                                                         Ca:6.0                                            11*   1/4    0.15   0.85           1.0  --   --   100                                                       Sr:6.0                                                                         Cd:6.0                                            12    9/20   0.25   0.75     --    --   --   --   100                          13    9/20   0.25   0.75     --    3.0  3.0  3.0  100                          14*   9/20   0.25   0.75     --    5.5  --   --    85                          15*   9/20   0.25   0.75     --    --   6.0  --   100                          16    9/20   0.25   0.75     --    --   --   --   100                                                       Ca:5.0                                            17    9/20   0.25   0.75           --   --   0.1  100                                                       Cd:5.0                                            18    1/2    0.35   0.65     --    1.0  2.0  --    95                          19    1/2    0.35   0.65     --    1.0  --   2.0  100                          20*   1/2    0.35   0.65     --    1.0  --   6.0  100                          21    3/4    0.40   0.60     --    --   5.0  5.0  100                          22*   1/2    0.40   0.60     Ba:22.0                                                                              3.0  3.0  --   100                                                       Ba:5.0                                            23    1/4    0.40   0.60           0.02 0.1  0.1   95                                                       Ca:5.0                                            24*   1/2    0.45   0.55     Sr:3.0                                                                               0.1  0.1  0.1  100                          ______________________________________                                    

Using the piezoelectric ceramics produced by the above method, there were prepared resonators with the radial extensional mode or thickness expansion mode in the following manner.

1. Preparation of radial extensional mode resonators:

The piezoelectric ceramic disk was provided with a silver electrode on its each surface and then polarized in an insulating oil maintained at a temperature of 20° to 200° C., by applying a DC electric field of 3.0-4.0 kv/mm between the electrodes.

2. Preparation of thickness expansion mode resonators:

The piezoelectric ceramic disk was lapped to obtain a thin disk with a thickness of 200 to 300 m. The resultant thin disk was provided with a silver electrode on each surface by the vapour deposition method, and polarized in an insulating oil maintained at a temperature of 20° to 200° C., by applying a DC electric field of 3.0-4.0 kv/mm between the electrodes. The silver electrodes was etched to form opposed circular electrodes having a diameter of 1-2 mm.

The thus prepared radial extentional mode resonators were subjected to the measurements of the permittivity (ε₃₃), electromechanical coupling factor (Kp) and mechanical quality factor (Qmp).

The thickness expansion mode resonators were kept in an oven for 1 hour at 150° C. to carry out the first heat aging, and then determined the electromechanical coupling coefficient (kt¹) and mechanical quality factor (Qmt). After that, the resonators were again kept in the oven under the same conditions to carry out the second heat aging, and then determined the electromechanical coupling coefficient (kt²).

It is to be noted that the heat aging is usually made just after the poling treatment in order to stabilize the piezoelectric properties so that the results after the second heat aging show the heat aging characteristics of the ceramics.

The dielectric constant (ε₃₃) of the radial extensional mode resonators and thickness expansion mode resonators were measured with a capacitance bridge and, the electromechanical coupling coefficients (Kp, Kt) and mechanical quality factor (Qmp, Qmt) were measured with the IRE standard circuits.

Results are shown in Table 2 together with a curie temperature for each sample.

In Tables 1 and 2, the asterisks (*) designate ceramics having a composition out of the scope of the present invention. Results for samples Nos. 1, 14, 15, 20, 22 and 24 are excluded from Table 2 since they provided no sintered bodies and exhibited no piezoelectric properties.

                  TABLE 2                                                          ______________________________________                                                   Extensional mode                                                                            Thickness expansion mode                                curie     resonator    resonator                                               Sample                                                                               temp.          Kp        Kt.sup.1                                                                            Kt.sup.2                                                                            change                                No.   (°C.)                                                                           ε.sub.33                                                                      (%)  Qmp  (%)  (%)  rate (%)                                                                              Qmt                            ______________________________________                                          1*   --      --     --   --   --   --   --     --                              2    485     182    5    110  25.6 24.8 3.1     82                             3    477     200    6    115  27.4 26.5 3.3     95                             4    456     218    8    613  30.1 29.1 3.3    418                             5    469     203    7    167  29.2 28.4 2.7    103                             6 475                                                                               205     7      173  29.5 28.6 3.1  107                                    7    452     224    10   106  32.4 31.2 3.7     90                             8    464     210    9    734  31.0 30.8 0.6    506                             9    421     233    15   133  34.1 32.6 4.4    100                            10    417     228    14   130  33.3 33.1 0.6     98                             11*  307     944    2    195  --   --   --     --                             12    424     216    15   134  35.1 33.9 3.4     85                            13    417     208    16   1721 35.7 35.5 0.6    956                             14*  --      --     --   --   --   --   --     --                              15*  --      --     --   --   --   --   --     --                             16    420     217    17   144  36.0 34.7 3.6    104                            17    411     208    17   152  35.9 35.8 0.3    106                            18    315     256    10   834  30.4 29.2 3.9    572                            19    308     243    11   792  30.9 30.7 0.6    547                             20*  --      --     --   --   --   --   --     --                             21    255     219    7    164  27.0 26.9 0.4    120                             22*  --      --     --   --   --   --   --     --                             23    203     353    6    155  25.1 25.0 0.4    101                             24*  --      --     --   --   --   --   --     --                             ______________________________________                                    

As will be evident from Tables 1 and 2, according to the present invention piezoelectric ceramics of the Pb(Sn.sub.α Sb₁₋α)O₃ -PbTiO₃ system can be produced which possess not less than 5% Kp and not less than 25% Kt and are small in the change rate of Kt resulting from the heat aging. The conventional air sintering method has such disadvantages that the sintering of the compositions of the Pb(Sn.sub.α Sb₁₋α)O₃ -PbTiO₃ system is ensured only in a limited, narrow compositional area and that the variation of α requires the alteration in the Pb(Sn.sub.α Sb₁₋α)O₃ content, while according to the present invention the sintering is ensured in a broader range of composition.

FIGS. 4 and 5 shows X-ray diffraction patterns for reaction products obtained by firing compositions corresponding to samples Nos. 7 and 13 at 1050° C. for 2 hours. As can be seen from these figures, the X-ray charts show peaks resulting from the presence of an unknown phase X in addition to the peaks resulting from PbTiO₃. In order to confirm this fact from another point of view, the forming bodies having compositions corresponding to samples Nos. 7 and 13 were calcined at various temperatures for 2 hours and then subjected to X-ray analysis to observe the state of the resultant products. Results are shown in FIG. 6. From this figure, it is confirmed that these compositions produce an unknown phase X in their reaction process and the phase X is present at temperatures within the range of about 600° C. to a temperature approximately equal to the temperature at which the sintering is completed.

From the above, it is concluded that the formation of the unknown phase X results from the component Pb(Sn.sub.α Sb₁₋α)O₃. For the identification of this unknown phase X, mixtures of raw materials were prepared to provide Pb(Sn.sub.α Sb₁₋α)O₃ wherein α takes a value of 0, 1/8, 1/4, 1/3, 1/2, 2/3, 3/4, 7/8 or 1. These mixtures were calcined at 900° C. for 2 hours, and the resultant products were determined with the X-ray analysis. Results are shown in Table 3.

                  TABLE 3                                                          ______________________________________                                         α            phasephasephase                                             ______________________________________                                         1                  PbSnO.sub.3                                                 7/8                PbSnO.sub.3 + X                                             3/4                X                                                           2/3                X                                                           1/2                X                                                           1/3                X                                                           1/4                X                                                           1/8                PbSb.sub.2 O.sub.6 + X                                      0                  PbSb.sub.2 O.sub.6                                          ______________________________________                                    

From Table 3, it is seen that the unknown phase X is produced as a single phase only when α takes a value within the range of 1/4 to 3/4. The single, unknown phase X with α=1/2 was indexed from the X-ray diffraction patterns. The results obtained are shown in Table 4. The unknown phase X has the face-centered cubic lattice with the lattice constant of 10.57 A.

                  TABLE 4                                                          ______________________________________                                         20 (deg.)* d (A)     hKl      S     I/I.sub.0 (0/0)                            ______________________________________                                         14.6       6.067     111       3    0.02                                       28.1       3.157     311      11    0.04                                       29.4       3.038     222      12    1.00                                       34.0       2.637     400      16    0.40                                       37.2       2.417     311      19    0.06                                                            511                                                       44.6       2.032     333      27    0.03                                       48.8       1.866     440      32    0.47                                       51.2       1.784     531      35    0.02                                       57.9       1.593     622      44    0.46                                       60.8       1.523     444      48    0.12                                       ______________________________________                                    

Identifying from the lattice constant and ionic radii of the constiruent ions, the unknowown phase X is a pyrochlore phase.

FIG. 7 shows X-ray diffraction patterns for a composition of Pb(Sn.sub.α Sb₁₋α)O₃ with α=1/2 which is the pyrochlore structure crystal phase. From the comparison between the X-ray diffraction patterns of FIG. 7 and those of FIGS. 4 and 5 it will be seen that the unknown phase X agrees with the pyrochlore phase. Taking acount of ionic radii of Pb²⁺ (1.24 A), Sn⁴⁺ (0.71 A), Sb⁵⁺ (0.62 A) and O⁻² (1.40 A) and the balance of their valencies, it is considered that in the system of Pb(Sn.sub.α Sb₁₋α)O₃ with α=1/2, this pyrochlore crystal structure may be expressed by the formula Pb²⁺ Sn⁴⁺ Sb⁵⁺ O_(13/2) ²⁻. Accordingly, the unknown phase X can be said to be a pyrochlore crystal phase with oxygen defect.

From the above particulars, the phase X having the pyrochlore crystal structure with oxygen defect may be expressed by the chemical formula Pb₂ Sn₂α Sb₂₋₂α O₇₋α wherein 1/4≦α≦3/4. This is supported by the facts that the measured density of porefree hot-pressed ceramics of Pb(Sn.sub.α Sb₁₋α)O₃ with α=1/2 is 8.50 to 8.52 g/cm³, that the theoretical density of Pb₂ SnSbO_(13/2) □_(1/2) is 8.52 g/cm³ provided that it has oxygen defect (when no oxygen defect is present the theoritical density is 8.61 g/cm³), and the results theoritically calculated from the diffraction intensity of X-ray diffraction patterns.

As disclosed above, the pyrochlore phase with oxygen defect promotes the solid reaction in the oxygen atmosphere, resulting in the formation of fine, dense ceramics with very low porosity and very small average pore size.

Scanning electron micrographs taken from natural surfaces of the samples Nos. 7 and 13 are shown in FIGS. 8 and 9, respectively. FIG. 10 is a scanning electron micrograph taken from a natural surface of a comparative sample having a composition PbTiO₃ +0.5 wt% Al₂ O₃ +0.5 wt% SiO₂. This comparative sample was prepared under the same firing conditions as those used for the preparation of samples Nos. 7 and 13. The oxygen concentration in the firing atmosphere was 100 vol%.

As is evident from these figures, the piezoelectric ceramics according to the present invention are composed of fine spherical grains with uniform grain size, while the conventional ceramic of the comparative sample is composed of large, variform grains. It results from that the formation of an intermediate phase, a pyrochlore phase with oxygen defect occurs for the Pb(Sn.sub.α Sb₁₋α)O₃ -PbTiO₃ system. As disclosed previously with reference to FIG. 5, this pyrochlore phase with oxygen defect, expressed by the formula Pb₂ Sn₂α Sb₂₋₂α O₇₋α, is formed at the grain boundaries in the early stage of the firing and is present up to an elevated temperature of about 1200° C. in the solid state. If the pyrochlore phase with oxygen defect is formed at the grain boundaries, it restraines grain growth and no pore agglomeration occurs, since its oxygen defects promotes the solid phase reaction and increases the mobility of oxygen gas at grain boudaries. In the final stage of the firing, this pyrochlore phase with oxygen defect transforms into the perovskite structure.

Thus, the present invention makes it possible to produce fine, dense piezoelectric ceramics with small pore size and very low porosity, which possess high mechanical strength, improved mechanical quality factor and high resistance to thermal shock. The piezoelectric ceramics produced according to the present invention have fine grain size less than 10μ and enables to put presently available designes into practice. For example, since the ceramics have high mechanical strength, they make it possible to produce thickness expansion mode resonators for very high frequency applications in which the ceramics used are required to have a thin thickness, for example, of about 200 microns at 10.7 MHz, about 80 microns at 27 MHz, or about 40 microns at 58 MHz. Further, when the ceramics are applied to vibrators for high power applications, they enables to obtain high mechanical energy by applying high voltage, since there is restraint of corona discharge which may occur in the pores.

Further, according to the present invention it is possible to obtain the following concomitant advantages. When industrially producing the ceramic ware or forming bodies it is the usual practice to incorporate an organic binder into the composition. This organic binder is subjected to combustion during the firing, and produces CO and CO₂ gas. Since CO gas has a reducing power, the reduction of PbO occurs. In addition, since the firing is carried out in the closed sagger, the combustion of the organic binder produces an oxygen-deficient atmosphere which has bad influence on the sintering of the ceramics. Such problems inherent to the conventional air sintering can be solved by the present invention. The electric and piezoelectric properties such as specific resistance, tan, dielectric constant are improved by 20 to 50%, compared with those obtained by the normal air firing method. Also, the scattering of these characteristics can be considerably reduced. When the piezoelectric ceramics produced by the present invention are applied to acoustic surface wave filters, the propagation loss of the acoustic surface waves is reduced by 1/2 to 1/3 times that obtained by the normal air firing method.

EXAMPLE 2

This example is given in explanation of piezoelectric ceramics for thickness expansion mode ceramic resonators. The compositions corresponding to that of sample No. 13 in Table 1 were used and test specimens were prepared in the same manner that described in example 1 except for the concentration of oxygen which are shown in Table 5.

For comparison, comparative samples were also prepared by the hot-pressed technique using the same composition that the above sample has. The hot-pressing conditions were 350 Kg/cm², 1200° C. and 2 hours.

Physical and mechanical properties of the resultant ceramics are shown in Table 5.

The bulk density of ceramics was determined with the Archimedes' method using polished specimens with a thin wax layer which were immersed in a liquid bath of hexachlorl, 3-butadiene (density=1.6829 g/cm³ at 20° C.). The results in the table are the average of 20 to 50 measurements for the each sample. The standard deviation (σ) is also sown in Table 5.

The pore sizes were determined with a reflecting microscope using polished specimens. The average grain sizes of the ceramics were determined with a scanning electron microscope using polished specimens which had been thermally etched at about 1200° C. for 1 hour in a lead oxide atmosphere. To determine the resistance to plastic deformation, the vickers' hardness was determined with a vickers' hardness tester (Model MVK, made by Akashi MFG. CO., LTD.) and calculated by the equation: ##EQU1## where θ=136°

d=diagonal line length for impression

p=load

                                      TABLE 5                                      __________________________________________________________________________                       Vichers                                                                             Deflective                                                                           grain                                                                              mean pore                                     Sample                                                                               O.sub.2 conc.                                                                       density                                                                               hardness                                                                            strength                                                                             size                                                                               size                                          No.   (vol %)                                                                             (g/cm.sup.3)                                                                          (kg/mm)                                                                             (kg/cm.sup.2)                                                                        (μ)                                                                             (μ)                                        __________________________________________________________________________     13-1  100  7.83 ( =0.01)                                                                         394  1015  ≈ 3                                                                        <1                                            13-2  80   7.82 ( =0.01)                                                                         390  1000  ≈3                                                                         <1                                            13-3* 50   7.70 ( =0.02)                                                                         236  594   ≈3                                                                         5˜10                                    13-4* 20 (air)                                                                            7.69 ( =0.03)                                                                         221  568   ≈3                                                                         6˜12                                    13-5* hot  7.84 ( =0.02)                                                                         405  1142  ≈1.5                                                                       <1                                                  pressing                                                                 R-1*  100  7.65 ( =0.03)                                                                         156  355   ≈12                                                                        9˜16                                    R-2*  90   7.62 ( =0.03)                                                                         147  350   ≈12                                                                        9˜16                                    R-3*  20 (air)                                                                            7.73 ( =0.04)                                                                         145  352   ≈12                                                                        9˜16                                    R-4*  hot  7.79 ( =0.02)                                                                         309  709   ≈5                                                                         <1                                                  pressing                                                                 __________________________________________________________________________

The deflective strength was determined with a universal testing machine using the three contact point method. The specimens were of 15 to 30 mm length, 3 to 5 mm width, and 0.5 to 3 mm thick. The average grain sizes were taken from the grains observed in the area of 100 square microns. The average pore sizes were determined from the number of pores and the areas of pores in 100 square microns provided that all the pores are of spherical.

Results for comparative samples made of a composition PbTiO₃ --0.5wt% Al₂ O₃ --0.5wt% SiO₂ of the prior art are also shown in Table 5. The test specimens of the comparative samples Nos. R-1 to R-3 were prepared by firing in oxygen atmospheres with oxygen concentration shown in Table 5 and those of the comparative sample No. R-4 were prepared by hot-pressing under the aforesaid condictions.

In Table 5, the data for the VICKERS' hardness, deffective strength, grain size and average pore size are the average of ten measurements and the asterisks (*) show the ceramics out of the scope of the present invention.

As can be seen from this table, the present invention makes it possible to produce piezoelectric ceramics with low porosity, small average pore size, and fine grain size comparable to those obtained by the hot-pressing. In addition, the ceramics obtained by the present invention have high vickers' hardness and high deflective strength comparable to those obtained by hot-pressing.

Reflecting micrographs of the ceramics are shown in FIGS. 11 to 14. In these figures, FIG. 11 shows a microstructure of sample No. 13-1 (×1000), FIG. 12 that of sample No. 13-3 (×200), FIG. 13 that of sample No. 13-5 (×1000), and FIG. 14 that of sample No. R-1 (×200). From these figures, it is observed that the ceramics obtained by the present invention have fewer pores and small pore size, comparable to those obtained by the hot-pressing.

FIGS. 15 and 16 are scanning electron micrographs of the ceramics of samples Nos. 13-1 and R-1, respectively. From these figures, it is clear that the ceramics obtained by the present invention have smaller pore size as compared with the comparative sample No. R-1. It is also understood that in the ceramics of PbTiO₃ --0.5wt% Al₂ O₃ --0.5wt% SiO₂ it is difficult to obtain small average pore size and fewer pores even if they are produced according to the present invention.

Although there is a fear of contamination with impurities such as Al₂ O₃, SiO₂ and so on which have been contained in the raw materials or atmosphere materials during manufacturing processes, such contamination is allowed in the process of the present invention: 

What I claim is:
 1. A method for producing piezoelectric ceramics of a Pb(Sn.sub.α Sb₁₋α)O₃ -PbTiO₃ system having a composition expressed by the general formula, xPb(Sn.sub.α Sb₁₋α)O₃ -yPbTiO₃, wherein subscripts α, x and y are mole fractions of the respective components and have the following values, x+y=1.00, 1/4≦α≦3/4, 0.01≦x≦0.40, and 0.60≦y≦0.99, which comprises, forming a powdered mixture of lead, tin, antimony and titanium compounds that correspond to said formula and which forms said composition at the firing temperature employed, calcining said mixture, forming said calcined mixture into a forming body and firing said body in an oxygen atmosphere containing not less than 80 volume percent of oxygen at a temperature of from 1000 to 1350 degrees C.
 2. The method according to claim 1 wherein the firing temperature is from 1100° to 1350° C.
 3. The method according to claim 1 wherein said oxygen atmosphere contains not less than 95 vol% of oxygen.
 4. The method according to claim 1 wherein a part of the lead in the composition is replaced with not more than 20 atomic percent of at least one element selected from the group consisting of Ba, Ca, Sr and Cd.
 5. The method according to claim 4 or claim 1 wherein said forming body is formed from fine particles of the components having average grain sizes of not more than 4 microns.
 6. The method according to claim 1 wherein said composition further contains manganese in oxide form and its content is not more than 5.0 wt percent when converted into MnO₂.
 7. The method according to claim 6 wherein said composition further contains chromium in the oxide form and its content is not more than 5.0 wt% when converted into Cr₂ O₃.
 8. The method according to claim 7 wherein said composition further contains magnesium in the oxide form, and the content of magnesium is not more than 5.0 wt% when converted into MgO.
 9. The method according to claim 1 wherein said composition further contains magnesium in oxide form and its content is not more than 5.0 wt percent when converted into MgO.
 10. The method according to claim 1 wherein said composition further contains chromium in oxide form and its content is not more than 5.0 wt percent when converted into Cr₂ O₃.
 11. The method according to claim 6 or 10 wherein said composition further contains magnesium in the oxide form and its content is not more than 5.0 wt% when converted into MgO. 